Metallisable trisazo dyestuffs



Unite METALLISABLE TRISAZO DYESTUFFS Werner Bossard, Riehen, near Base], and Jiirg Ammann, Basel, Switzerland, assignors to J. R. Geigy A.-G., Basel, Switzerland, 21 Swiss firm No Drawing. Application November 21, 1955 Serial No. 548,262

Claims priority, application Switzerland December 3, 1954 6 Claims. (Cl. 260-157) dyestulfs having afiinity to cellulose fibres are obtained if u 1 mol of a tetrazotised 4.4-diamino-3.3'-dialkoxydiphenyl is coupled first with 1 mol of an o-hydroxybenzene carboxylic acid and then with 1 mol of a monoazo dyestuif of the general Formula I H 038 NH:

in which B represents a 2.3-azolo-1-phenyl radical.

Chiefiy 4.4'-diarnino-3.3-dimethoxydiphenyl but also if desired 4.4-diamino-3.3'-diethoxyor -3.3-dicarboxy methoxy-diphenyl can be used as tetrazo components in the process according to the present application.

o-Hydroxybenzene carboxylic acids, advantageously 2- hydroxybenzene-l-carboxylic acid, are used as the first coupling component. However, their reactive homologues and derivatives substituted in the ring can also be used, for example the 3- or 4-methyl2-hydroxy-benzene-1- carboxylic acid, 3.6-dimethyl-2hydroxybenzene-l-carboxylic acid, 3-chloro-Z-hydroxybenzene-l-carboxylic acid, 4-methoxy or 4-aminoor 4-acetamino-2-hydroxybenzene-1-carboxylic acid.

The monoazo dyestuffs corresponding to the above Formula I which can be coupled and which are used as azo components in the second step are obtained by acid coupling of Z-primary amino-5-hydroxynaphthalene-7- sulphonic acid with a diazotised 2.3-azolo-1-aminobenzene compound which contains the amino group in the neigh;

bouring position to a nitrogen atom of the hetero-ring and preferably in the neighbouring position to an imino group or to a tertiary ring N-atom which by tautomeric re- HOOC tats atefl azo' compound described above.

arrangement can form an imino group. Such monoazo dyestuffs of the above formula are obtained, for example from diazotised 7-amino-indoles, 7-amino-indazoles, 7- amino-benzirnidazoles, 7-amino-benztriazoles:, which may possibly be further substituted by the usual atoms and groups in aromatic substances, e. g. by halogen, alkyl, aralkyl, phenyl, carboxyl, nitro, acylamino, sulphonic acid amide, alkyl sulphone groups, by acid coupling with 2 primary amino 5 hydroxynaphthalene-7-sulphonic acid.

The coupling of the monoazo diazo compounds obtained under the usual conditions in the first step with the monoazo dyestuff of the general Formula I, .is performed in an alkaline medium, for example in the presence of sodium carbonate or of ammonia and if necessary of tertiary organic nitrogen bases such as pyridine and triethanolarnine which accelerate the coupling.

in the form of their water soluble alkali or ammonium salts, the new trisazo dyestuffs are dark powders which dissolve in water according to the composition with a more or less dull violet colour and in concentrated sulphuric acid with a blue-black colour. They dye cellulose fibres from a liquor containing Glaubers salts in violetblack shades. Black dyeings which are fast to wet and light are obtained by treating the dyeings with agents giving off copper. The coppering can be performed in the dyebath or in a fresh bath. The usual inorganic or organic copper salts such as copper sulphate, copper chloride, copper acetate and, possibly also complex copper salts such as result from ammonia, organic amines or from certain aliphatic hydroxy fatty acids in an alkaline medium, can be used for this purpose. Sometimes, suitable trisazo dyestuffs according to the present invention can also be treated in substance with agents giving off metal.

The following examples illustrate the invention without limiting it in any way. Where not otherwise stated, parts are given as parts by weight and the temperatures are in degrees centigrade. The relationship of parts by Weight to parts by volume is as that of kilogrammes to litres.

Example 1 24.4 parts of tetrazotised 4.4'-diamino-3.3 '-dimethoxydiphenyl are coupled in the presence of 30 parts of sodium carbonate with 17 parts of 2-hydroxy-4-methylbenzene-1- carboxylic acid to form the intermediate product.

At the same time 14.8 parts of l-methyli-aminobenztriazole are dissolved in excess hydrochloric acid and an aqueous solution of 6.9 parts of sodium nitrite are added while stirring well at 02. After a few minutes, a weak acid to litmus paper solution of 23.9 parts of 2-amino-5- hydroxynaphthalene-7-sulphonic acid and 5.3 parts of sodium carbonate in 200 parts of water are added while cooling with ice to this diazo solution. On completion of the coupling, the red monoazo dyestuff in a weakly alkaline solution is coupled at 0-5 with the diazo mono- The trisazo dyestuif formed is precipitated with sodium chloride, filtered off i and dried. The dark powder of the formula:

H O OCH:

n, Hots NH:

N-CH

J dissolves in water with a blacleviolet colour and in concentrated sulphuric acid with a blue-black colour. Cellulose dyeings after being coppered are black and they have very good wet and light fastness properties.

If in this example 19.2 parts of 4-amino'benztriazolyll-acetic acid, 15.1 parts of 4-aminopiazothiole or 15 parts of 4-aminobenzthiazole, 22.4 parts of 4-amino-6- methoxybenzthiazole-2-carboxylic acid or 148 parts of 2-rnethyl-4-aminobenzoxazolone are used instead of 14.8 parts of 1*methyl-4-aminobenztriazole, and otherwise the same procedure is followed, then dyestuifs with similar shades and properties are obtained.

Example 2 24.4 parts of 4.4-dia-mino-3.3'-dimethoxydiphenyl are tetrazotised in the usual way and coupled with 15.3 parts of 'Z hydroxybenZene-l-carboxylic acid and 30 parts of sodium carbonate to form the diazo monoazo dyestuft. At the same time 13.4 parts of 7-aminobenztriazole are dissolved in excess hydrochloric acid and 6.9 parts of sodium nitrite dissolved in a little water are quickly added while stirring very quickly at 0-2. A weakly acid to litmus papersolution of 23.9 parts of Z-amino-S-hydroxynaphthalene-'7-sulphonic acid and 5.3 parts of sodium carbonate in 200 parts of water is gradually added. The coupling proceeds without difiicu1ty;it can be accelerated by the careful dropwise addition of an aqueous sodium acetate solution until the reaction is Weakly mineral acid. The monoazo dyestuif which, in an alkaline to litmus paper medium, has been precipitated with sodium chlofide and isolated by filtration, is dissolved in 600 parts of water and 150 parts by volume of pyridine .and is then coupled in the presence of excess sodium carbonate at 045 with the brown-red suspension of the above monoazo diazo compound. The trisazo dyestuii of the formula:

HOOC 01120 no N=N methyl-7-aminobenztriazole are used, then a dyestuff with similar good properties is obtained.

Example 3 5 The monoazo diazo compound according to Example 2 from 24.4 parts of tetrazotised .4.4'-diamino-3.3'-dimethoxydiphenyl .and 15.3 parts of Z-hYdIOXYbenZene-I-carboxylic acid is poured under ice cooling into the aqueous solution of the red monoazo d-yestuit obtained by coupling in an acid medium 17:8 parts of .diazotised 7-aminobenztriazole-S-carboxylic acid with 239 parts of Z-amino-S- hydroxynaPhthaleneJ-sulphonic acid, the solution also containing parts of sodium carbonate. As soon as the coupling to form the trisazo dyestuif is complete, this is precipitated with sodium chloride, filtered oft and dried. The dyestuif is a dark powder. It corresponds to the formula:

and dissolves in water with a dark violet and in concentrated sulphuric acid with a blue-black colour. The aftercoppered dyeings of cellulose fibres are deep black and have excellent wet and light fastness properties.

If in this example the .Z-hydroxybenzene-l-carboxylic acid is replaced by 17 parts of 2-hydroxy-3- or -4-methylbenzene-l-carboxylic acid, 19.2 parts of 2-hydroxy-3- chlorobenzenel-carboxylic acid, 21.5 parts of 'Z-hydroxy- 4-acetylaminobenzened-carboxylic acid, 18.6 parts of 2- hydroxy-4-methoxybenzene-l-carboxylic acid or 18.4 parts of '2-hydroxy'3:6-dimethylbenzene-1-carboxylic acid and the 7-aminobenztriazole=5 carboxylic acid is replaced 'by 21.4 parts of 7-arninobenztriazole-5-sulphonic acid or by 21.2 parts of "7-arninobenztriazoleeS-methyl sulp'hone and otherwise the same procedure is followed, then dyestufis with similar properties are obtained.

Example .4

24.4pa1'ts of 4.4'-diamino-'-3.3"-dimethoxydiphenyl are Nan,

tetrazotised in hydrochloric acid solution with 13.8 parts of sodium nitrite and the tetrazo compound obtained is coupled in the presence of 30 parts of sodium carbonate with 17 parts of 2-hydroxy-3-methy1benzene-l-carboxylio acid. The red-brown suspension of the diazo monoazo compound is poured at 0-5 into the sodium carbonate 75 alkaline solution of the red monoazo dyestufi obtained by mineral acid coupling of 13.3 parts of diazotised 7- parts of 2-rnethyl-7-aminobenzimidazole.or -16.1;parts of amino-indazole with 23.9 parts of Z-amino-S-hydroxy- 2.5-dimethyl-7-aminobenzimidazole or 19.1 parts of 2 naphthalene-7-sulphonic acid. As soon as the coupling methyl-7-aminobnzimidazole-S-carboxylic acid or 2217 to form the trisazo dyestutf of the formula: parts of 2-methyl-7-aminobenzimidazoled sulplionic acid.

H000 OHaO OOH! 011 HO- N=N N=N on H038 NH:

HN NH is complete, the dyestutf is precipitated by the addition of or 28.9 parts of Z-phenyl-7-aminobenzimida2ole-S-sub a little sodium chloride, filtered ofi, washed and dried. phonic acid are used. It is a dark powder which dissolves in water with a dull I violet and in concentrated sulphuric acid with a blue- Example 6 black colour. The cellulose dyeings which, on being after coppered are black, have excellent wet and light fastness properties.

If in this example, 14.7 parts of 5-methyl-7-aminoindazole, 14.7 parts of 6-rnethyl-7-amino-indazole, 21.3 parts of 7-amino-indazole-4-sulphonic acid, 13.2 parts of 7-amino-indole, 17.6 parts of 7-amino-indole-2-carboxylic acid, 19 parts of 3-methyl-7-arnino-indole-Z-carboxylic acid or 17.3 parts of 2-ethyl-3-methyl-7-amino-indole are used instead of 13.3 parts of 7-amino-indazole, and otherwise the same procedure is followed, then dyest-ufis with similar properties are obtained.

2 parts of the dyestuil obtained according to Example 2 are dissolved in a dyebath containing 3000 parts of water and 2 parts of sodium carbonate. 100 parts of cotton are entered at -50", the bath is heated within 30 minutes to 9095, 30 parts of sodium sulphate are added and dyeing is performed for minutes at .this temperature. After this time, the dyed goods are rinsed cold and after treated in a fresh bath with 2 parts of crystallised copper sulphate in 2000 parts of water and 2 parts of 30% acetic acid for 30 minutes :at The goods are rinsed and dried in the usual way. The black cotton dyeing has excellent fastness properties. Example 5 What we claim is:

The diazo monoazo compound produced according to 35 A msazo dyestufi havmg the general formula: Example 2 from 24.4 parts of tetrazotised 4.4'-diamino- H0 C1110 (Refit 3.3-dirnethoxydiphenyl and 15.3 parts of Z-hydroxybenzene-l-carboxylic acid is poured at 05 into a solution, AN=N O containing sodium carbonate, of the monoazo dyestufi H000 obtained by acid coupling of 13.3 parts of diazotised 7- 40 B015 NH! aminobenzimidazole with 23.9 parts of Z-amino-S-hydroxynaphthalene-7-sulphonic acid in 600 parts of water and parts by volume of pyridine. After the coupling, 1 which occurs quickly, the trisazo dyestufl of the formula:

H000 0H3? OOH: OH

H0|S- NHq 01a is precipitated with sodium chloride, filtered off and dried. wherein:

The dark powder dissolves in water with black-violet and in concentrated sulphuric acid with a blue-black colour. On after treating the dark violet direct 'dyeings with 60 a copper salts, they become black and have very good wet and light fastness properties.

Further dyestuffs with similar properties are obtained A represents an aromatic radical of the benzene series containing the hydroxy and carboxyl group in the 0- position to each other, and

B represents a 2.3-azolo-l-phenyl radical containing an imino group in neighbouring position to the azo linkage.

if, instead of 13.3 parts of 7-aminobenzirnidazole, 14.7 2. A trisazo dyestuff of the formula:

H000 CHzO OCH; OH

HO; NH:

N=NQ N time Qyesmfi c the formula:

4. A trisazo dyestufi of the formula:

K000 CHgO OCH: OH

5. A dyestufi of-the formula:

HQQC 0 00H:

6. A trisazo kqyesiuff of the formula:

Q OOH OCH: OCH:

H-N I \N References Cited in the file of this patent UNITED STATES PATENTS 2,390,480 West Dec. 4, 1945 2,507,754 Bossard et al May 16, 1950 FOREIGN PATENTS 191,738 Switzerland Sept, [16. 1.937 220,116 Switzerland 15, 194;; 

1. A TRISAZO DYESTUFF HAVING THE GENERAL FORMULA: 